Chlorinated paraffin wax amines for controlling fungi and bacteria



Patented Sept. 7, 1948 2,448,910 CHLORINATED PARAFFIN WAX AMINES FOR CONTROLLING TERIA FUNGI AND BAC- Thomas E. Reamer, Albany, Calif., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application March 27, 19M, Serial N- 528,348

7 Claims. 1 v The presentinventi-on relates to the control of micro biological pests and pertains particularly to compositions for and methods of pre-" ventingfungicidal and bactericidal attack on textiles, such as cotton.

A special problem often encountered is the prevention of disintegration of textiles, especially cotton, due to attack by mould fungi and bacteria. It is particularly diflicult to prevent biological decay and loss of strength in textiles that may be exposed to severe weathering, since fungi and bacteria which attack textiles are widely distribilted in nature. For example, the most commonly occurring types are species of Aspergillus and Penicillium, together with various Fungi Imperfiecti such as Cladosporium and Stemphylium. In the past, in order to prevent decay of textiles, it has generally been necessary to use waterproofing treatments, such as impregnations with bitumens, waxes, rubber compounds, etc. Other treatments, such as with copper naphthenate and other similar materials, have also been proposed. However, these treatments are not fully satisfactory for various reasons, including the shortness of the period of effective prevention, low efficiency, attack of the textiles by the agents themselves, etc.

It is therefore a general object of the present invention to provide more efficient fungicidal and bactericidal compositions.

It is another object of this invention to provide a method of controlling micro biological pests, such as-fungi-and bacteria.

Anpbject of the invention is to provide a treating composition and method for preventing attack on cellulosic materials and proteins by fungi and bacteria. Specifically, it is an object to pro= tect textiles exposed to severe weathering conditions.

It has now been found that relatively high molecular weight ali chloroamines (including allphatic and alicyclic, i. e., non-benzenoid chloroamines), and mixtures containing these compounds are highly effective fungicides and bactericides, especially in preventing biological decay and disintegration of textiles exposed to severe weather conditions, particularly under conditions of high moisture, such as burial in or contact with wet soil. Such compounds contain at least 12, and preferably 20-40, or more carbon atoms; preferably two oleflnic double bonds; at least one, preferably two or more amino groups: and at least one non-ionizable chlorine atom. It is further desirable that the compound contain an oleophilichydrocarbon radical of 8 carbon 2 atoms or more, this radical preferably being unsaturated and attached to an amino group. The amino-groups may be primary, secondary and tertiary, and are preferably attached. to other than terminal carbon atoms. may also contain other inorganic substituents,

such as hydroxy, cyan'o, thiocyano, nitro, car= bonyl, ether, thioether, mercapto, etc. The present agents may be used as the free base.

As examples .of suitable higher molecular weight unsaturated all chloroamines, the following may be mentioned: chloro amino cetane,

' chloro amino hexadecane, diamino chloro cetene,

diamino chloro eicosene; di N dimethyl amino) chloro octadecene; triamino ethyl methyl chloro= isopropyl dedecene; diamino chloromethyl isobutyl methyl cetene; diamino chloro triacontylene; N-ethyl methyl chlorohexyl amino propyl cyclohexenylamine; chloro amino tetra-ismbutylene, etc. v

Suitable mixtures of compounds may be obtained by incomplete ammonolysis of chlorinated hydrocarbons of at least 2 carbon atoms and more than 2, and preferably 3 or more, chlorine atoms. Suitable hydrocarbons include, for example, hard and soft paramn wax, Vaseline, transformer oil, various lubricating oils and other mineral oils having more thanabout 12 carbon atoms. Parafilnic or naphthenic oils or both are suitable and their aromatic content should preferably be relatively low. a

An especially effective agent is obtained from paraflln wax by chlorination and ammonolysis, the former reaction being conducted at a temperature of about C. to C. until a chlorine content of about 15%, and preferably about 25-38%, is reached; andthe latter reaction taking place at about C. to C. under an ammonia gas pressure of about 300-500 pounds per square inch in the presence of a solvent such as ethyl alcohol. The resulting product normally has a molecular weight range of 450-600, contains per molecule 1.2-2.5 amino groups of which about 75% are primary and secondary and the remainder tertiary amino groups, 1-2 olefinic double bonds, and about 0.5-1.5 non-ionizable chlorine atoms. It is obtained at about a 50-50 mixture of the free base and the hydrochloride saltof the latter. In the following description such a free base or the like will be referred to as chlorinated paraffin wax amines," or wax amines? for short. A more detailed description of a method for preparing the present wax amines will aid in practicing the present inven- 55 tion, which method is as follows: a parafilnic The compounds than comprising a large proportion of monolysis is completed. Thus, for example. 8%- zable components is chlorinated in the 10% of ammonia may be dissolved in the solvent base at a temperature of 100 C.-125 C. prior to the introduction of the chlorinated hychlorine content above 15% is reached. drocarbon or, if desired, the solution of chlorinorinated product is ammonolyzed, prefated hydrocarbon in the solvent is first brought a the presence of a solvent, at a temperato the reaction temperature and the amount of we 14:0"- C. and the amines thus formed ammonia necessary to produce the desired in- .rated. The hydrocarbon material should crease in pressure is thereafter introduced. Ammolecular weight above250 and prefermonolysis may be carried out at temperatures ween 350 and about 800 and should conbetween about 135 C. and 200C. At temperasubstantial proportion of crystallizable tures below 140 .C. the ammonolysis proceeds very The nature of the hydrocarbons deslowly. At temperatures above about 175 C. it 5 to a large extent the properties of the proceeds very rapidly but the amines obtained do produced by this process. If ahydrocarnot possess as good bonding properties. Thus Ltaining less than 90% of crystallizable 15 temperatures from 140 C. to 175 C. and particuis'used, it is often advantageous to sublarly from 150 C. to 160 C. are preferred for best rior to chlorination to a de-oiling operaresults. Ammonolysis is continued at least until h as sweating, crystallization from a 501- substantially complete, 1. e. until it does not proparation with the aid of a dewaxing solceed further at an appreciable rate and most of :has propane or a mixture of dimethyl the chlorine combined with the hydrocarbon has or acetone with benzol or toluene, etc., been displaced, but may be continued if convento increase the concentration of crysient for longer periods up to 10-15 hours; 3-6 e components. The properly selected hyhours, in general, sumce. If desired, soaking at in material is chlorinated with gaseous the reaction temperature may advantageously be without the use of special catalysts under prolonged, i. e., may be continued for 10-15 hours. as insuring thorough and uniform contact The resulting product contains amines thus for example, bubbling the gas into the formed, excess ammonia, the solvent and am- Jydrocarbon through a porous plate, and monium chloride, the latter being largely insolugitation of the reaction mixture. The ble in the mixture. Part of the amines are free, n may be conducted under moderate and the other part in the form of hydrochloride mospheric pressures in an autoclave, but salts. After completion of ammonolysis, the crysferred to efiect it in a vessel maintained tals of ammonium chloride are separated as by lbstantially atmospheric pressure. After conventional filtration, and if desired the amtion is completed, it is advantageous to mania, together with the solvent may be recovered reaction mixture of dissolved chlorine 5 from the filtrate by distillation for further use in ochloric acid, for example, by applying the process. The amines thus separated are obor passing therethrough an inert gas such tained in partially neutralized form. Free amines ocarbon gas, carbon dioxide, hydrogen, or difierent salts may be prepared therefrom by etc. If this step is omitted, part of the conventional methods. a employed in the followin operation is 40 Although the unsaturated chloro-co'ntaining ly neutralized or oxidized. The chlorinpolyamine mixtures are preferred, many other lrocarbon is then dissolved in a suitable groups of polyamines may be used, among which preferably methyl or ethyl alcohol; the are the alpha branched aliphatic primary polysolution is treated with ammonia under amines, having more than 12 carbon atoms, which at elevated temperature. Suitable solare derived from aliphatic mono-oleflns by hyust possess solvent power for both the drochlorination and ammonolysls, and may be :ed hydrocarbon and ammonia and must referred to as "alpha methyl amines" or "alpha ically inert under conditions of ammoamines.

Water-soluble ethers, alcohols such as In some cases, mixtures of compounds containl'ycerol, propanol, tertiary butanol, secing among them the essential groups maybeused. pentanol, dimethyl, di-ethyl, methyl- Thus, there may be used a mixture of compounds ethyl-propyl ether, monoor di-methyl containing per average molecule more than one her, mono-, dior tri-methyl glycerol amino group, more than one double bond, 0.5 to -ethylene dioxide, etc., and particularly 1.5 non-ionizable chlorine atoms, and an oleond ethyl alcohol are among the suitable philic hydrocarbon chain of at least 8 carbon If desired, they may contain up to about atoms linked to amino group. For example, er. The commercial azeotrope of ethyl there may be mentioned mixtures of higher mond water, containing about 5% of water, lecular weight aliphatic polyamines having an 'st practical solvent due to its availability oleophilic hydrocarbon chain of at least 8 carof recovery. At room temperature chlo- 6o bon atoms and unsaturated aliphatic chlorides. wax is but little soluble therein but at For use in treating textiles, according to th'e ures above about 120 C. it dissolves preferred application of the agents of the present .wo to five volumes of'the solvent are i invention, volatile and readily vaporizable solsufficient. Ammonolysis is preferably vents may be used as carriers for said agents. :1 in an' autoclave allowing moderate Suitable carriers include, for example, aliphatic, f the reacting mixture, particularly at araliphatic, and aromatic organic solvents, such ning of the reaction to produce uniform as mineral or petroleum spirits, carbon tetrachlo- The necessary quantity of ammonia is ride, ethylene dichloride, dichloro diethyl ether, at least l-2 equivalents of the chlorine di-isopropyl ether, petroleum ether naphtha. If the hydrocarbon. In order that the kerosene, ethylene glycol, benzene, toluene, alcotnay proceed at a reasonable speed and hols, acetone, mixtures thereof and the like, aqueritial completion, it is desirable that the ous solutions or suspensions, etc. Aside from ressure of ammonia be maintained at readily vaporizable solvents, materials such as 00 p. s. i. and preferably from 150 to 200 viscous oils, various polymers and plastic resins, ring the entire time, i. e. until the amcreosote oils, water-proofing emulsions such as oi aluminum acetate, soap, and wax, etc, may also be used as carriers for the present agents. Generally about -35% of the present agents are dissolved or suspended in the carrier, although more or less may be used, depending on the character of the carrier and agent used. Other agents, toxic or otherwise, may also be incorporated in the carrier. For example, insect repellents or insecticides, such as dichloro dlphenyl trichloro ethane, phenothiazine, etc., emulsifiers, coloring agents, perfumes, etc., may be added to the carrier.

- In treating textiles, such as cotton, linen, jute, bagasse and the like, including keratinous textiles and fabrics, such as wool, the present agents may be applied thereto by dipping, spraying, or brushing with solutions of the agents, preferably in a volatile solvent, such as benzene. As a rule, at least 2 or 3% and generally more than by weight (on the basis of treated cloth) of the agents are applied to the cloth. Preferred is the impregnation of the textile with to 30% or more of the present agents, such as the wax amines.

After the textiles have been treated with the present agents, they may be subsequently treated with other agents for various purposes. For example, a chloro polyamine treated fabric or mesh may be impregnated with bituminous material in forming a reinforced asphaltic revetment lining.

The present method of preventing attack on textiles by fungi and bacteria may be applied to fish-nets, canvas-goods, such as tents, awnings, ground-sealing covers, etc., burley sacks used for sand-bags, fabrics used in reinforcing revetment linings of asphalt and the like, etc.

The agents of this invention together with certain similar but ineffective agents were tested for prevention of attack by fungi and bacteria on heavy cotton canvas under severe weathering conditions in the following manner. Canvas swatches were impregnated with the cloth preservatives and duplicate samples buried in garden loam maintained moist at 90 F, At the end of 3 months for one series and 6 months for another series the soil was carefully removed and the condition of the cloth determined. The results of these tests are shown in the following table:

6 1 about 22% wax amine-85 lbs., and after 3 months burial of the treated sample86 lbs.

Besides being useful as a toxicant or repellent in textile preserving compositions, these chloro 5 polyamines may also be used to control various organisms, particularly fungi and bacteria, in wood, soil, plants, seeds, etc. For use in wood pre servatives, the present agents may be dissolved or suspended in preferably clear petroleum oils, cre- 10 sylic acids (1. e. alkyl phenols which may boil between about 200-350 0.), volatile organic solvents, aqueous solutions, etc. with or without the addition of other wood preservatives and applied to wood by impregnation, spraying, brushing, etc.

For agricultural use on and in soils, the agents may be incorporated in a volatile organic solvent, aqueous liquid, etc. with or without the addition of other soil treating agents, such as soil fumigants, e. 3. lower unsaturated polychlorides of the allyl-vinyl type, mixtures of saturated and unsaturated polychloro hydrocarbons of 3 to 4 carbon atoms, etc., or such 'as fertilizers, e. g. liquid or gaseous ammonia, etc., and applied to the soil by spraying on the surface,-injecting 25 below the surface, or distributing with irrigation water.

For use on plants, the present agents may be dissolved or suspended in plant mineral spray oils and emulsified in water to produce sprayable emulsions, or the agents without oil may be emulsifled or suspended in water to produce plant sprays. Any suitable emulsifying agent, such as partial esters of poiyhydric alcohols, e. g. glycerol mono-oleate, polyethylene glycol mono laurate,

palmitate, stearate, oleate, etc., various soaps, alkali metal salts of sulfuric acid mono esters and organic sulfuric acids and the like, may be used in combination with such sprays. In general, the emulsifying agents are used in sufllcient amount to resist for a suitable period the tendency of some of the present agents to reverse the emulsions. Likewise, some of the present agents are sumciently surface-active so that the agents themselves will act as the emulsifier, thereby avoiding the necessity of using a separate emulsiher. If desired, the present agents may also be absorbed on finely-divided solid materials, such as wood flour, talc, clay, sulfur, carbon black,etc., to be used as fungicidal dusts.

1 ll Length reserve ve Preservative (b on of Test Condition of Cloth Swatch wt. of treated Period cloth) Mos. None None 6 Com gletely disintegrated.

no naphthonate l7. 1; 20. 4 6 o. Creosote 43. 9; 43. 2 6 Do. As halt 56. 2; 54. 0 6 Partially disintegrated; no tensile strength. Asphalt cutback (RC). 50. 8; 53.4 6 Do. Do 45. 5: 45. 3 6 Do. Chlorinated parafiln wax amines (free base) 26. 8; 25. 8 6 Unaffected. n-Octadecylamine 17. 0; l8. 1 6 Cloth completely disintegrated. Laury l-pyridinium-bromide. 3. 0 6 Do. None None 6 Do. I As halt cutback (RC) containing 3% wax Q. 0 6 Cloth very weak but not disintegrated.

am s.

It will be seen from the data that wax amines, in the form of the free bases, are surprisingly superior to other cloth preservatives, the canvas swatches treated therewith being virtually unaffected by the severe conditions of the burial. In fact, the tensile strength of a wax amine treated sample remained substantially the same. For example, the tensile strengths of a inch wide canvas swatch after various treatments were as follows: untreated-75 lbs., after treatment with Besides being useful in themselves as a toxicant or repellent, the compounds of the present invention may be used in conjunction with wellknown insecticides and fungicides. Thus, they may also be used in combination with rotenone, pyrethrum, lead arsenate, nicotine, thiocyanates, copper naphthenate, unsaturated cyclic ketols, such as di-isophorone, dichloro dlphenyl trichloro ethane and the like.

I claim as my invention:

1. A method of controlling fungi and bacteria comprising exposing them to mixtures of allphatic compounds having at least 12 carbon atoms and not more than about 40 carbon atoms and containing per average molecule more than one amino group, at least one olefinic double bond, combined chlorine only in the form of 0.5 to 1.5 non-ionizable chlorine atoms, and an oleophilic hydrocarbon chain of at least 8 carbon atom-s linked in an amino group.

2. A method of controlling fungi and bacteria in their attack on celiulosic and protein materials which comprises applying to said materials at least 2% by weight of paraflln wax amines containing per average molecule more than one amino group, at least one oleflnic double bond, 0.5 to 1.5 combined chlorine atoms only in the form of non-ionizable chlorine atoms, and a molecular weight from 450 to 600.

3. A method of controlling fungi and bacteria comprising exposing them to mixtures of aliphatic compounds having at least 12 carbon atoms and not more than about 40 carbon atoms and containing per average molecule more than one amino group, at least one olefinic double bond, and combined chlorine only in the form of from 0.5 to 1.5 non-ionizable chlorine atoms.

4. A method of controlling fungi and bacteria comprising exposing them to mixtures of aliphatic compounds containing per average molecule more than one amino group, at least one olefinic double bond, combined chlorine only in the form of from 0.5 to 1.5 non-ionizable chlorine atoms, and a molecular weight from 450 to 600.

5. A method of controlling fungi and bacteria 'in their attack on textile materials which comprises applying to said materials at least 2% by weight of a mixture of aliphatic compounds having at least 12 carbon atoms and not more than about 40 carbon atoms and containing per average molecule more than one amino group, at least one olefinic double bond, and combined chlorine only in the form of from 0.5 to 1.5 non-ionizable chlorine atoms.

6. A textile article comprising in combination a textile substantially uniformly impregnated with at least 2% by weight of a mixture of aliphatic compounds having at least 12 carbon atoms and not more than about 40 carbon atoms and containing per average molecule more than one amino group, at least one olennic double bond, and from 0.5 to 1.5 combined chlorine atoms only in the form of non-ionizable chlorine atoms.

7. A textile article comprising in combination a textile substantially uniformly impregnated with at least 2% by weight of chlorinated paraflln wax airlines containing per average molecule more than one amino group, at least one oleflnic double bond, 0.5 to 1.5 combined chlorine atoms only in the form of non-ionizable chlorine atoms, and a molecular weight from 450 to 600.

THOMAS E. REAMER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Organic Chemistry by Karrer, 193a, page 113, published by Nordeman Publishing Co. Inc., New York, N. Y. 

